DOE OSTI2020
LiNi3P2 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are twelve inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six P3- atoms to form distorted LiP6 pentagonal pyramids that share corners with three LiP5 square pyramids, corners with twelve NiP4 tetrahedra, edges with twelve NiP4 tetrahedra, and faces with two equivalent LiP6 pentagonal pyramids. There are a spread of Li–P bond distances ranging from 2.71–2.84 Å. In the second Li1+ site, Li1+ is bonded to five P3- atoms to form LiP5 square pyramids that share corners with four LiP6 pentagonal pyramids, corners with four LiP5 square pyramids, corners with eight NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one NiP5 square pyramid, and edges with seven NiP4 tetrahedra. There are a spread of Li–P bond distances ranging from 2.45–2.54 Å. In the third Li1+ site, Li1+ is bonded to five P3- atoms to form distorted LiP5 square pyramids that share corners with four LiP6 pentagonal pyramids, corners with four LiP5 square pyramids, corners with eight NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one NiP5 square pyramid, and edges with seven NiP4 tetrahedra. There are a spread of Li–P bond distances ranging from 2.44–2.55 Å. In the fourth Li1+ site, Li1+ is bonded to six P3- atoms to form distorted LiP6 pentagonal pyramids that share corners with four LiP5 square pyramids, corners with twelve NiP4 tetrahedra, an edgeedge with one LiP5 square pyramid, edges with nine NiP4 tetrahedra, and faces with two equivalent LiP6 pentagonal pyramids. There are a spread of Li–P bond distances ranging from 2.70–2.75 Å. In the fifth Li1+ site, Li1+ is bonded to six P3- atoms to form distorted LiP6 pentagonal pyramids that share corners with two equivalent LiP5 square pyramids, corners with twelve NiP4 tetrahedra, edges with two LiP5 square pyramids, edges with nine NiP4 tetrahedra, and faces with two equivalent LiP6 pentagonal pyramids. There are a spread of Li–P bond distances ranging from 2.72–2.78 Å. In the sixth Li1+ site, Li1+ is bonded to six P3- atoms to form distorted LiP6 pentagonal pyramids that share corners with two NiP5 square pyramids, corners with three LiP5 square pyramids, corners with twelve NiP4 tetrahedra, edges with twelve NiP4 tetrahedra, and faces with two equivalent LiP6 pentagonal pyramids. There are a spread of Li–P bond distances ranging from 2.72–2.84 Å. In the seventh Li1+ site, Li1+ is bonded to five P3- atoms to form distorted LiP5 square pyramids that share corners with four LiP6 pentagonal pyramids, corners with two equivalent LiP5 square pyramids, corners with two equivalent NiP5 square pyramids, corners with eight NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one LiP5 square pyramid, and edges with seven NiP4 tetrahedra. There are a spread of Li–P bond distances ranging from 2.45–2.56 Å. In the eighth Li1+ site, Li1+ is bonded to five P3- atoms to form LiP5 square pyramids that share corners with four LiP6 pentagonal pyramids, corners with two equivalent LiP5 square pyramids, corners with two equivalent NiP5 square pyramids, corners with eight NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one LiP5 square pyramid, and edges with seven NiP4 tetrahedra. There are a spread of Li–P bond distances ranging from 2.45–2.55 Å. In the ninth Li1+ site, Li1+ is bonded to five P3- atoms to form distorted LiP5 square pyramids that share corners with four LiP6 pentagonal pyramids, corners with two equivalent LiP5 square pyramids, corners with eight NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one LiP5 square pyramid, edges with two equivalent NiP5 square pyramids, and edges with seven NiP4 tetrahedra. There are a spread of Li–P bond distances ranging from 2.41–2.55 Å. In the tenth Li1+ site, Li1+ is bonded to six P3- atoms to form distorted LiP6 pentagonal pyramids that share corners with two equivalent LiP5 square pyramids, corners with two equivalent NiP5 square pyramids, corners with twelve NiP4 tetrahedra, an edgeedge with one NiP5 square pyramid, edges with two LiP5 square pyramids, edges with nine NiP4 tetrahedra, and faces with two equivalent LiP6 pentagonal pyramids. There are a spread of Li–P bond distances ranging from 2.72–2.76 Å. In the eleventh Li1+ site, Li1+ is bonded to six P3- atoms to form distorted LiP6 pentagonal pyramids that share corners with two equivalent NiP5 square pyramids, corners with four LiP5 square pyramids, corners with twelve NiP4 tetrahedra, an edgeedge with one LiP5 square pyramid, an edgeedge with one NiP5 square pyramid, edges with nine NiP4 tetrahedra, and faces with two equivalent LiP6 pentagonal pyramids. There are a spread of Li–P bond distances ranging from 2.71–2.76 Å. In the twelfth Li1+ site, Li1+ is bonded to five P3- atoms to form distorted LiP5 square pyramids that share corners with four LiP6 pentagonal pyramids, corners with two equivalent LiP5 square pyramids, corners with eight NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one LiP5 square pyramid, edges with two equivalent NiP5 square pyramids, and edges with seven NiP4 tetrahedra. There are a spread of Li–P bond distances ranging from 2.42–2.55 Å. There are thirty inequivalent Ni+1.67+ sites. In the first Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with four LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, a cornercorner with one NiP5 square pyramid, corners with ten NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, edges with two LiP5 square pyramids, and edges with three NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.22–2.30 Å. In the second Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, corners with three LiP5 square pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, and edges with four NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.24–2.29 Å. In the third Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one LiP5 square pyramid, and edges with four NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.18–2.29 Å. In the fourth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with four LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, a cornercorner with one NiP5 square pyramid, corners with ten NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, edges with two LiP5 square pyramids, and edges with three NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.22–2.27 Å. In the fifth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, corners with three LiP5 square pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one NiP5 square pyramid, and edges with four NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.23–2.29 Å. In the sixth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with two equivalent NiP5 square pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one LiP5 square pyramid, and edges with four NiP4 tetrahedra. There are one shorter (2.18 Å) and three longer (2.29 Å) Ni–P bond lengths. In the seventh Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one LiP5 square pyramid, and edges with four NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.23–2.29 Å. In the eighth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, corners with four LiP5 square pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, and edges with four NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.20–2.29 Å. In the ninth Ni+1.67+ site, Ni+1.67+ is bonded in a 5-coordinate geometry to five P3- atoms. There are a spread of Ni–P bond distances ranging from 2.33–2.75 Å. In the tenth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with four LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with ten NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one NiP5 square pyramid, edges with two LiP5 square pyramids, and edges with three NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.21–2.28 Å. In the eleventh Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, corners with three NiP5 square pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one LiP5 square pyramid, and edges with four NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.20–2.29 Å. In the twelfth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, corners with four LiP5 square pyramids, corners with ten NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one NiP5 square pyramid, and edges with four NiP4 tetrahedra. There are one shorter (2.20 Å) and three longer (2.28 Å) Ni–P bond lengths. In the thirteenth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with four LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with ten NiP4 tetrahedra, an edgeedge with one LiP6 pentagonal pyramid, an edgeedge with one NiP5 square pyramid, edges with two LiP5 square pyramids, and edges with three NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.21–2.29 Å. In the fourteenth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with twelve NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one LiP5 square pyramid, and edges with three NiP4 tetrahedra. There are two shorter (2.20 Å) and two longer (2.34 Å) Ni–P bond lengths. In the fifteenth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with two equivalent LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with twelve NiP4 tetrahedra, edges with three LiP6 pentagonal pyramids, an edgeedge with one LiP5 square pyramid, and edges with three NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.20–2.34 Å. In the sixteenth Ni+1.67+ site, Ni+1.67+ is bonded in a 5-coordinate geometry to five P3- atoms. There are a spread of Ni–P bond distances ranging from 2.32–2.72 Å. In the seventeenth Ni+1.67+ site, Ni+1.67+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with four LiP6 pentagonal pyramids, a cornercorner with one LiP5 square pyramid, corners with ten NiP4 tetrahedr